N-bromodichloroacetamide



United States Patent 0 2,713,596 N-BROMODICHLOROACETAIVHDE Joseph D. Park and John R, Lacher, Boulder, Colo., and Henry J. Gerjovich, Wilmington, DeL, assignors to Arapahoe Chemicals, Inc., Boulder, -Colo., a corporation of Colorado No Drawing. Original application rial No. 249,388. Divided and this application December 28, B53, Serial No. 412,958

1 Claim. (Cl. 260-561) October 2, 1951,

This invention relates to a novel brominating agent, namely N-bromodichloroacetamide.

Objects and advantages of the invention will be set I forth in part hereinafter and in part will be obvious herefrom, or may be learned by practice with the invention, the same being realized and attained by means'of the compound pointed out in the appended claim.

An object of this invention is to prepare a novel brominating agent which can be utilized in a variety of chemical reactions.

Our novel brominating agent, N-bromodichloroacetamid may In order to illustrate the invention more clearly, the following example is given.

EXAMPLE To a solution of 0.1 mole of silver oxide in 250 ml. of anhydrous trifiuoroacetic acid, was added 0.2 mole of dichloroacetamide. The reaction mixture was stirred under 1 mm. pressure, 29 g. (60% of the theoretical amount) of N- bromodichloroacetamide was obtained. The N-bromodichloroacetamide obtained in a 76% yield had a melting point of 96 C.

Our novel compound possesses unique brominating properties heretofore unknown and unpredictable on the basis of the prior art. These properties will become character of the bromine atom. In this study it was observed that cyclohexene reacts with N- bromotrichloroacetamide (Equation 1) to yield predominantly N-( 2 bromocyclohexyl)-trichloroacetamide; with Nbromodichloroacetamide (Equation 2) the product is largely 3-bromocyclohexene; with N-bromomonochloroacetamide (Equation 3) the product is predomi- 2,713,596 Patented July 19, 1955 nantly 1,2-dibromocyclohexane. In contrast with these results, is the bromination of cyclohexene with N-bromoacetamide (Equation 4), where a 3-bromoeyclohe'xene was obtained.

produced the same product as did the unsubstituted acetamide. One would have react with toluene to produce monobrominated toluenes in yields of 50 to 72%, the constitution of the monobrominated toluenes is very diiferent in each case.

CH3 CHzBr BrNHCOCXa HnNCOOXa HzNCOCXs 0 and p isomers It will be seen from the data presented in Table I that unsubstituted N-bromoacetamide produces a monobrominated toluene which is entirely the result of reaction with the side-chain (Equation 5), while the monosubstituted N-bromoacetamide produces almost entirely nuclear substitution (Equation 6). The diand trisubstituted compounds produce both nuclear and side-chain bromination, with the trisubstituted N-bromoacetamide being most like the unsubstituted N-bromoacetamide.

Table I BROMINATION OF 'IOLUENE AT 90-103" 0.

Type of Substitu- Percent tion Conver- Compound Msiongo P one 170- eicent Percent motoluenes Side- Nuclear chain N-bromoacetamide 50 0 100 N-bromomonochloroacetamide 72 82 18 N-bromodlchloroacetamide 64 64 36 N-bromotrichloroacctamide 58 17 83 From the above studies, is evident that the chemical behavior of the N-bromodichloroacetamide compared to the N-bromomonochloroacetamide and N-bromotrichloroacetamide could not have been predicted on the basis of classical organic chemistry.

Our novel brominating agent may be utilized in various organic reactions as mild and specific oxidizing agents.

The invention in its broader aspects is not limited to the specific steps and compositions described but departures may be made therefrom within the scope of the accompanying claim Without departing from the principles of the invention and without sacrificing its chief advantages.

This application is application Serial No.

We claim:

N-bromodichloroacetamide.

a divisional application of pending 249,388, filed October 2, 1951.

References Cited in the file of this patent 

